The present invention relates to liquid crystalline media and to liquid crystal displays comprising these media, preferably to displays operating in the TN mode and in particular to TN displays addressed by an active matrix.
Liquid Crystal Displays (LCDs) are widely used to display information. Still the most widely used electro-optical mode is the twisted nematic (TN)-mode. Besides this mode also displays using the super twisted nmatic (STN)- and the electrically controlled birefringence (ECB)-mode with their various modifications, as well as others. Besides these modes, which all do use an electrical field, which is substantially perpendicular to the substrates, respectively to the liquid crystal layer, there are also electro-optical modes employing an electrical field substantially parallel to the substrates, respectively the liquid crystal layer, like e.g. the in-plane switching (IPS)-mode (as disclosed e.g. in DE 40 00 451 and EP 0 588 568).
A further promising electrooptical mode for LCDs is the optically compensated bend (OCB) mode. This mode has a favorable small viewing angle dependence of the contrast. Further the response times in this mode are small.
Especially for micro displays operating in the TN-mode, fast switching cells have to be realized. For this task the cell gap preferably is reduced, which in turn requires liquid crystalline media with higher values of the birefringence.
Preferably TN-cells are operated with an optical retardation corresponding the first transmission minimum according to Gooch and Tarry.
Liquid crystal mixtures consisting predominantly or even entirely of terminally cyano substituted biphenyls and terphenyls are as a rule characterized by suitable high xcex94xcex5 values, but have limited values of xcex94n and already are likely to show insufficient stability at low temperatures, i.e. in most cases either formation of a smectic phase and or crystallization. Liquid crystal mixtures using large quantities of halogenated tolane compounds with three phenyl rings, which are almost dielectrically neutral, are disclosed, e.g. in the European Patent Application No. EP 99111782.1 are characterized by comparatively low xcex94xcex5 values which are not suitable for most applications and often even show severe problems with respect to the stability of the nematic phase at low temperatures.
Thus, there is a significant need for liquid crystal media with suitable properties for practical applications such as a wide nematic phase range, low viscosities, appropriate optical anisotropy xcex94xcex5 according to the display mode used especially a suitably high xcex94n for OCB displays and for composite systems like PDLCs and in particular with suitably large good compatibility with polymer precursors for composite systems.
Surprisingly, it now has been found that liquid crystal media with high xcex94n especially useful for fast switching TN AMD displays can be realized, which do not exhibit these drawbacks of the materials of the prior art or at least do exhibit them to a significantly lesser degree.
These improved liquid crystal media according to the instant application are realized by comprising at least two components:
a first liquid crystal component (called component A),
comprising compounds of formula I, which are compounds with very high values of xcex94n, preferably of 0.15 or more, more preferably 0.15 to 0.80, more preferably 0.20 to 0.60, more preferably of 0.22 or more and most preferably of 0.25 to 0.55.
wherein
R11 and R12 are, independently of one another, n-alkyl, n-alkoxy with 1 to 7 C atoms, preferably 2 to 5 C atoms, alkenyl, alkenyloxy or alkoxyalkyl with 2 to 7 C atoms, preferably with 2 to 5 C atoms, preferably alkyl, alkenyl or alkoxy, especially preferred n-alkyl or n-alkoxy,
at least one of 
xe2x80x83and the others of 
xe2x80x83each, independently of each other, are 
xe2x80x83and alternatively 
xe2x80x83may also be 
one of Z11 and Z12 is xe2x80x94Cxe2x89xa1Cxe2x80x94 and the other one, if present, is xe2x80x94Cxe2x89xa1Cxe2x80x94,xe2x80x94CH2Oxe2x80x94, xe2x80x94CF2Oxe2x80x94, xe2x80x94OCF2xe2x80x94 trans- xe2x80x94CHxe2x95x90CHxe2x80x94, trans- xe2x80x94CFxe2x95x90CFxe2x80x94, xe2x80x94COOxe2x80x94 xe2x80x94CH2xe2x80x94CH2xe2x80x94, xe2x80x94CF2xe2x80x94CF2xe2x80x94 or a single bond, preferably a single bond and
n is 0 or 1,
preferably 
xe2x80x83when present, is 
xe2x80x83or their mirror images,
and/or preferably 
xe2x80x83or their mirror images,
and/or preferably 
xe2x80x83or their mirror images,
and simultaneously a second component (component B) comprising one or more dielectrically positive compounds of formula II 
wherein
R2 has the meaning given for R11 under formula I above, 
xe2x80x83each independently have the meaning given for 
above under formula I
Z21 Z22 are independently of each other xe2x80x94CH2CH2xe2x80x94, xe2x80x94COOxe2x80x94, trans- CHxe2x95x90CHxe2x80x94, trans- xe2x80x94CFxe2x95x90CFxe2x80x94, xe2x80x94CH2Oxe2x80x94, xe2x80x94CF2Oxe2x80x94 or a single bond, preferably at least one of them is a single bond, most preferably both are a single bond,
X2 is, F, Cl, CF3, OCF2H or OCF3, preferably F or OCF3, most preferably F and
m is 0, 1 or 2
and optionally a third component (component C) which comprises dielectrically neutral compounds of formula Ill 
wherein
R31 and R32 each, independently of each other, have the meaning given for R11 under formula I above,
Z31 and Z32 are, independently of each other, xe2x80x94CH2CH2xe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94, trans- CHxe2x89xa1CHxe2x80x94, trans- xe2x80x94CFxe2x95x90CFxe2x80x94, xe2x80x94CH2Oxe2x80x94, xe2x80x94CF2Oxe2x80x94 or a single bond, preferably a single bond, 
xe2x80x83each independently have the meaning given for 
above under formula I
k is 0 or 1
and optionally a fourth component (component D) which comprises dielectrically neutral compounds of formula IV 
wherein
R41 and R 42 independently of each other, have the meaning given above under formula I for R11, 
Z4 are, independently of each other, xe2x80x94CH2CH2xe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94Cxe2x89xa1Cxe2x80x94 or a single bond, preferably a single bond and
o is 0 or 1.
Preferably the liquid crystalline media according to the instant invention contain a component A comprising, preferably predominantly consisting of and most preferably entirely consisting of compounds of formula I.
Comprising in this application means in the context of compositions that the entity referred to, e.g. the medium or the component, contains the compound or compounds in question, preferably in a total concentration of 10% or more and most preferably of 20% or more.
Predominantly consisting, in this context, means that the entity referred to contains 80% or more, preferably 90% or more and most preferably 95% or more of the compound or compounds in question.
Entirely consisting, in this context, means that the entity referred to contains 98% or more, preferably 99% or more and most preferably 100.0% of the compound or compounds in question.
The compounds of formula I are preferably selected from the group of sub-formulae I-1 to I-7
wherein
R11 and R12 have the meaning given under formula I above
Y11 and Y2 are, independently of each other, H or F.
In a preferred embodiment the liquid crystalline media according to the instant invention contains a component B comprising, preferably predominantly consisting of and most preferably entirely consisting of compounds of formula II.
The compounds of formula II are preferably selected from the group of sub-formulae II-1 to II-7
wherein
R2, X2 and 
xe2x80x83have the respective meanings given under formula II above and preferably
R2 is n-alkyl or 1-E-alkenyl,
X2 is F or OCF3 and 
Y21, Y22 and Y23 are, independently of each other, H or F.
In a further preferred embodiment the liquid crystal medium contains a liquid crystal component C which is preferably predominantly consisting of and most preferably entirely consisting of compounds of formula III
The compounds of formula III are preferably selected from the group of sub-formulae III-1 to III-6
wherein
R31, R32, Z31, 
xe2x80x83each have the meaning given for 
under formula I above, and preferably
R31 and R32 are, independently of each other, n-alkyl, n-alkoxy or 1-E-alkenyl,
Z31 is xe2x80x94COOxe2x80x94, xe2x80x94CH2xe2x80x94CH2xe2x80x94, trans- xe2x80x94CHxe2x95x90CHxe2x80x94, trans- xe2x80x94CFxe2x95x90CFxe2x80x94, xe2x80x94CF2Oxe2x80x94, xe2x80x94CH2Oxe2x80x94 or a single bond, preferably xe2x80x94COOxe2x80x94 or a single bond, 
Y31, Y32 and Y33 are, independently of each other, H or F.
This component C may be present, and preferably is present, besides component B.
In a further preferred embodiment the liquid crystal medium contains a liquid crystal component D which is preferably predominantly consisting of and most preferably entirely consisting of compounds of formula IV
The compounds of formula IV are preferably selected from the group of sub-formulae IV-1 to IV-4
wherein
R41,R42 and 
xe2x80x83have the meaning given under formula IV above and preferably
R41 is n-alkyl,
R42 is alkoxy and 
Most preferably the medium contains compounds of formula I selected from the group of sub-formulae I-1 to I-3 and I-5 to I-7. Most preferably of sub-formula I-7 and in particular of sub-formula I-7a, given above,
wherein
R11 and R12 have the respective meanings given under formula I above, and preferably are, independently of each other, n-alkyl with 1 to 5 C atoms or n-alkoxy with 1 to 4 C atoms, or 1-E-alkenyl with 2 to 5 C atoms.
Preferably component B comprises one or more compounds selected from the group of compounds of sub-formulae II-3a to II-3h, II-6a to II-6f and II-7a to II-7c 
wherein
R2 has the meaning given under formula II above and preferably is alkyl with 1 to 5 C atoms, alkoxy with 1 to 4 C atoms or 1-E-alkenyl with 2 to 5 C atoms.
Preferably component C comprises one or more compounds selected from the group of compounds of sub-formulae Ill-1a, III-2a, III-3a, III-3b III-5a and III-5b 
wherein
R31 and R32 have the respective meanings given under formula III above, and preferably R31 is n-alkyl or 1-E-alkenyl and R32 is n-alkyl, alkoxy or alkenyl, preferably both with 1, respectively 2, to 5 C atoms.
Preferably component D comprises one or more compounds selected from the group of compounds of formula IV-1, as given above, and sub-formulae IV-2a and IV-2b 
wherein
R41 and R42 have the meaning given under formula IV above and preferably R41 is n-alkyl and R42 is alkoxy.
Preferably the media according to the present invention are composed as follows, in % by weight.
Component A is used in a concentration from 5 to 50%, preferably from 15 to 45% and most preferably from 25 to 40% of the total mixture.
Component B is used in a concentration from 15 to 65%, preferably from 25 to 60% and most preferably from 35 to 55% of the total mixture.
Component C is used in a concentration from 0 to 50%, preferably from 10 to 40% and most preferably from 15 to 35% of the total mixture.
Component D is used in a concentration from 0 to 40%, preferably from 2 to 30% and most preferably from 3 to 20% of the total mixture.
The media according to the present invention optionally contain further compounds, which are used to adjust especially the phase range and the optical anisotropy of the media.
The total concentration of these further compounds in the liquid crystal medium according to the present invention is preferably 0 to 30%, more preferably 0 to 25%, most preferably 0 to 15% and in particular 5 to 10%.
Preferably the liquid crystal medium contains 50% to 100%, more preferably 70% to 100% and most preferably 80% to 100% and in particular 90% to 100% totally of components A, B, C and D, which, in turn, contain, preferably predominantly consist of and most preferably entirely consist of one or more of compounds of formulae I, II, III and IV, respectively.
The liquid crystal media according to the instant invention are characterized by a clearing point of 70xc2x0 C. or more, preferably of 80xc2x0 C. or more, especially preferred of 85xc2x0 C. or more and in particular of 90xc2x0 C. or more.
The xcex94n of the liquid crystal media according to the instant invention is 0.14 or more, preferably 0.17 or more, preferably in the range from 0.18 to 0.35, more preferably in the range from 0.19 to 0.30, most preferably in the range from 0.20 to 0.28 and in particular in the range from 0.20 to 0.25.
The xcex94xcex5, at 1 kHz and 20xc2x0 C., of the liquid crystal medium according to the invention is preferably 5 or more, preferably 6 or more, most preferably 8 or more and in particular 10 or more.
Preferably the nematic phase of the inventive media extends at least from 0xc2x0 C. to 70xc2x0 C., most preferably at least xe2x88x9220xc2x0 C. to 70xc2x0 C. and most preferably at least from xe2x88x9230xc2x0 C. to 80xc2x0 C., wherein at least means that preferably the lower limit is under cut, whereas the upper limit is surpassed.
In the present application the term dielectrically positive compounds describes compounds with xcex94xcex5 greater than 1.5, dielectrically neutral compounds are compounds with xe2x88x921.5 xe2x89xa6xcex94xcex5xe2x89xa61.5 and dielectrically negative compounds are compounds with xcex94xcex5 less than xe2x88x921.5. The same holds for components. xcex94xcex5 is determined at 1 kHz and 20xc2x0 C. The dielectrical anisotropies of the compounds is determined from the results of a solution of 10% of the individual compounds in a nematic host mixture. The capacities of these test mixtures are determined both in a cell with homeotropic and with homogeneous alignment. The cell gap of both types of cells is approximately 10 xcexcm. The voltage applied is a rectangular wave with a frequency of 1 kHz and a root mean square value typically of 0.5 V to 1.0 V, however, it is always selected to be below the capacitive threshold of the respective test mixture.
For dielectrically positive compounds the mixture ZLI-4792 and for dielectrically neutral, as well as for dielectrically negative compounds, the mixture ZLI-3086, both of Merck KGaA, Germany are used as host mixture, respectively. The dielectric permittivities of the compounds are determined from the change of the respective values of the host mixture upon addition of the compounds of interest and are extrapolated to a concentration of the compounds of interest of 100%.
Components having a nematic phase at the measurement temperature of 20xc2x0 C. are measured as such, all others are treated like compounds.
The term threshold voltage refers in the instant application to the optical threshold and is given for 10% relative contrast (V10) and the term saturation voltage refers to the optical saturation and is given for 90% relative contrast (V90) both, if not explicitly stated otherwise. The capacitive threshold voltage (V0, also called Freedericksz-threshold VFr) is only used if explicitly mentioned.
The ranges of parameters given in this application are all including the limiting values, unless explicitly stated otherwise.
Throughout this application, unless explicitly stated otherwise, all concentrations are given in mass percent and relate to the respective complete mixture, all temperatures are given in degrees centigrade (Celsius) and all differences of temperatures in degrees centigrade. All % values for prepartians of components are by weight unless indicated otherwise. All physical properties have been and are determined according to xe2x80x9cMerck Liquid Crystals, Physical Properties of Liquid Crystalsxe2x80x9d, Status Nov. 1997, Merck KGaA, Germany and are given for a temperature of 20xc2x0 C., unless explicitly stated otherwise. The optical anisotropy (xcex94n) is determined at a wavelength of 589.3 nm. The dielectric anisotropy (xcex94xcex5) is determined at a frequency of 1 kHz. The threshold voltages, as well as all other electro-optical properties have been determined with test cells prepared at Merck KGaA, Germany. The test cells for the determination of xcex94s had a cell gap of 22 xcexcm. The electrode was a circular ITO electrode with an area of 1.13 cm2 and a guard ring. The orientation layers were lecithin for homeotropic orientation (xcex5||) and polyimide AL-1054 from Japan Synthetic Rubber for homogeneuous orientation (xcex5xe2x8axa5). The capacities were determined with a frequency response analyser Solatron 1260 using a sine wave with a voltage of 0.3 Vrms. The light used in the electro-optical measurements was white light. The set up used was a commercially available equipment of Otsuka, Japan. The characteristic voltages have been determined under perpendicular observation. The threshold (V10)-mid grey (V50) - and saturation (V90) voltages have been determined for 10%, 50% and 90% relative contrast, respectively.
The liquid crystal media according to the present invention can contain further additives and chiral dopants in usual concentrations. The total concentration of these further constituents is in the range of 0% to 10%, preferably 0.1% to 6%, based on the total mixture. The concentrations of the individual compounds used each are preferably in the range of 0.1 to 3%. The concentration of these and of similar additives is not taken into consideration for the values and ranges of the concentrations of the liquid crystal components and compounds of the liquid crystal media in this application.
The inventive liquid crystal media according to the present invention consist of several compounds, preferably of 3 to 30, more preferably of 5 to 20 and most preferably of 6 to 14 compounds. These compounds are mixed in conventional way. As a rule, the required amount of the compound used in the smaller amount is dissolved in the compound used in the greater amount. In case the temperature is above the clearing point of the compound used in the higher concentration, it is particularly easy to observe completion of the process of dissolution. It is, however, also possible to prepare the media by other conventional ways, e.g. using so called pre-mixtures, which can be e.g. homologous or eutectic mixtures of compounds or using so called multi-bottle-systems, the constituents of which are ready to use mixtures themselves.
By addition of suitable additives, the liquid crystal media according to the instant invention can be modified in such a way, that they are usable in all known types of liquid crystal displays, either using the liquid crystal media as such, like TN-, TN-AMDs, ECB- or VAN-AMDs, IPS- and OCB-LCDs and in particular in TN-AMDs.
The melting point T(C,N), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T (N,I) of the liquid crystals are given in degrees centigrade (Celsius).
In the present application and especially in the following examples, the structures of the liquid crystal compounds are represented by abbreviations also called acronyms. The transformation of the abbreviations into the corresponding structures is straight forward according to the following two tables A and B. All groups CnH2n+1, and CmH2m+1, are straight chain alkyl groups with n respectively m C atoms. The interpretation of table B is self evident. Table A does only list the abbreviations for the cores of the structures. The individual compounds are denoted by the abbreviation of the core followed by a hyphen and a code specifying the substituents R1, R2, L1 and L2 follows:
The liquid crystal media according to the instant invention contain preferably
seven or more, preferably nine or more, compounds selected from the group of compounds of tables A and B and/or
four or more, preferably five or more, compounds selected from the group of compounds of table B and/or
four or more, preferably six or more, compounds selected from the group of compounds of table A.
The entire disclosure[s] of all applications, patents and publications, cited above or below, and of corresponding European Application No. EP 01101237.4, filed Jan. 19, 2001, is hereby incorporated by reference.